Atomic-resolution imaging of surface and core melting in individual size-selected Au nanoclusters on carbon.

Although the changes in melting behaviour on the nanoscale have long attracted the interest of researchers, the mechanism by which nanoparticles melt remains an open problem. We report the direct observation, at atomic resolution, of surface melting in individual size-selected Au clusters (2-5 nm diameter) supported on carbon films, using an in situ heating stage in the aberration corrected scanning transmission electron microscope. At elevated temperatures the Au nanoparticles are found to form a solid core-liquid shell structure. The cluster surface melting temperatures, show evidence of size-dependent melting point suppression. The cluster core melting temperatures are significantly greater than predicted by existing models of free clusters. To explore the effect of the interaction between the clusters and the carbon substrate, we employ a very large-scale ab initio simulation approach to investigate the influence of the support. Theoretical results for surface and core melting points are in good agreement with experiment.

Experimental determination of the energy difference between competing isomers of deposited, size-selected gold nanoclusters.

The equilibrium structures and dynamics of a nanoscale system are regulated by a complex potential energy surface (PES). This is a key target of theoretical calculations but experimentally elusive. We report the measurement of a key PES parameter for a model nanosystem: size-selected Au nanoclusters, soft-landed on amorphous silicon nitride supports. We obtain the energy difference between the most abundant structural isomers of magic number Au561 clusters, the decahedron and face-centred-cubic (fcc) structures, from the equilibrium proportions of the isomers. These are measured by atomic-resolution scanning transmission electron microscopy, with an ultra-stable heating stage, as a function of temperature (125-500 °C). At lower temperatures (20-125 °C) the behaviour is kinetic, exhibiting down conversion of metastable decahedra into fcc structures; the higher state is repopulated at higher temperatures in equilibrium. We find the decahedron is 0.040 ± 0.020 eV higher in energy than the fcc isomer, providing a benchmark for the theoretical treatment of nanoparticles.

Note: Production of silver nanoclusters using a Matrix-Assembly Cluster Source with a solid CO2 matrix.

One of the main limitations to the application of clusters on applied areas is the limited production; therefore, it is of great interest to up scale cluster production while keeping good size control. The Matrix-Assembly Cluster Source is a new high flux cluster source, which exploits cluster formation inside a solid rare gas matrix that is sputtered by an ion beam. Clusters are formed and ejected in this process. Here we report the production of Ag clusters when the rare gas is replaced by CO2 for the matrix formation at 20 K. Size distributions were determined from scanning transmission electron microscopy analysis of samples with four different metal loadings, 4%, 8%, 14%, and 23% of Ag atoms to CO2 molecules, and two ion beam energies, 1 keV and 2 keV. Cluster mean size showed weak dependence on metal loading, being ≈80 atoms for the first three concentrations, whereas the change in ion beam energy has caused cluster mean size to shift from 86 to 160 atoms. The results are interpreted in terms of bonding energy between Ag and CO2 and compared to the rare gas (Ar) matrix.

Initiating and imaging the coherent surface dynamics of charge carriers in real space.

The tip of a scanning tunnelling microscope is an atomic-scale source of electrons and holes. As the injected charge spreads out, it can induce adsorbed molecules to react. By comparing large-scale 'before' and 'after' images of an adsorbate covered surface, the spatial extent of the nonlocal manipulation is revealed. Here, we measure the nonlocal manipulation of toluene molecules on the Si(111)-7 × 7 surface at room temperature. Both the range and probability of nonlocal manipulation have a voltage dependence. A region within 5-15 nm of the injection site shows a marked reduction in manipulation. We propose that this region marks the extent of the initial coherent (that is, ballistic) time-dependent evolution of the injected charge carrier. Using scanning tunnelling spectroscopy, we develop a model of this time-dependent expansion of the initially localized hole wavepacket within a particular surface state and deduce a quantum coherence (ballistic) lifetime of ∼10 fs.

Note: Proof of principle of a new type of cluster beam source with potential for scale-up.

We introduce a new type of cluster beam source based on the assembly of (metal) clusters within a condensed (rare gas) matrix. The "Matrix Assembly Cluster Source" employs an ion beam to enhance collisions between metal atoms in the matrix and to sputter out clusters to form a beam. We demonstrate the formation and deposition of gold and silver nanoclusters with mean size tunable from a few atoms to a few thousand atoms. The cluster flux is equivalent to a current nanoAmp regime but potentially scalable to milliAmps, which would open up a number of interesting experiments and applications.

The size-dependent morphology of Pd nanoclusters formed by gas condensation.

Size-selected Pd nanoclusters in the size range from 887 to 10,000 atoms were synthesized in a magnetron sputtering, inert gas condensation cluster beam source equipped with a time of flight mass filter. Their morphologies were investigated using scanning transmission electron microscopy (STEM) and shown to be strongly size-dependent. The larger clusters exhibited elongated structures, which we attribute to the aggregation, through multiple collisions, of smaller clusters during the gas phase condensation process. This was confirmed from the atomically resolved STEM images of the Pd nanoclusters, which showed smaller primary clusters with their own crystalline structures.

Atomically resolved real-space imaging of hot electron dynamics.

The dynamics of hot electrons are central to understanding the properties of many electronic devices. But their ultra-short lifetime, typically 100 fs or less, and correspondingly short transport length-scale in the nanometre range constrain real-space investigations. Here we report variable temperature and voltage measurements of the nonlocal manipulation of adsorbed molecules on the Si(111)-7 × 7 surface in the scanning tunnelling microscope. The range of the nonlocal effect increases with temperature and, at constant temperature, is invariant over a wide range of electron energies. The measurements probe, in real space, the underlying hot electron dynamics on the 10 nm scale and are well described by a two-dimensional diffusive model with a single decay channel, consistent with 2-photon photo-emission (2PPE) measurements of the real time dynamics.

Pt Diffusion Dynamics for the Formation Cr-Pt Core-Shell Nanoparticles.

Layered core-shell bimetallic Cr-Pt nanoparticles were prepared by the formation and later reduction of an intermediate Pt-ion-containing supramolecular complex onto preformed Cr nanoparticles. The resultant nanoparticles were characterized by X-ray diffraction analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, and aberration-corrected scanning transmission electron microscopy. The results are consistent with the presence of Pt diffusion during or after bimetallic nanoparticle formation, which has resulted in a Pt/Cr-alloyed core and shell. We postulate that such Pt diffusion occurs by an electric-field-assisted process according to Cabrera-Mott theory and that it originates from the low work function of the preformed oxygen-defective Cr nanoparticles and the rather large electron affinity of Pt.

Transformations of citrate and Tween coated silver nanoparticles reacted with Na2S.

Silver nanoparticles (Ag NPs) are susceptible to transformations in environmental and biological media such as aggregation, oxidation, dissolution, chlorination, sulfidation, formation/replacement of surface coatings following interaction with natural organic matter (NOM). This paper investigates the impact of surface coating and Suwannee River fulvic acid (SRFA) on the transformations and behavior of Ag NPs (citrate coated and Tween coated; cit-Ag NPs and Tween-Ag NPs, respectively), following reaction with different concentrations of Na2S solution (as a source of sulfide species, H2S and HS(-)). These transformations and the dominant mechanisms of transformations were investigated using UV-vis and scanning transmission electron microscopy coupled with electron energy loss spectroscopy. Here, we have shown that Ag NP surface coating impacts their dissolution following dilution in ultrahigh purity water, with higher extent of dissolution of Tween-Ag NPs compared with cit-Ag NPs. Tween-Ag NPs are susceptible to dissolution following their sulfidation at low S/Ag molar ratio. Suwannee River fulvic acid (SRFA) slows down the dissolution of Tween-Ag NPs at low sulfide concentrations and reduces the aggregation of cit-Ag NP in the presence of sodium sulfide. Sulfidation appears to occur by direct interaction of sulfide species with Ag NPs rather than by indirect reaction of sulfide with dissolved Ag species subsequent to dissolution. Furthermore, the sulfidation process results in the formation of partially sulfidized Ag NPs containing unreacted (metallic) subgrains at the edge of the NPs for Tween-Ag NPs in the presence of high sulfide concentration (2000nM Na2S), which occurred to less extent at lower Na2S concentration for Tween-Ag NPs and at all concentrations of Na2S for cit-Ag NPs. Thus, sulfidized Ag NPs may preserve some of the properties of the Ag NPs such as their potential to shed Ag(+) ions and their toxic potential of Ag NPs.

Mapping the site-specific potential energy landscape for chemisorbed and physisorbed aromatic molecules on the Si(1 1 1)-7 × 7 surface by time-lapse STM.

We present a scanning tunnelling microscope study of site-specific thermal displacement (desorption or diffusion) of benzene, toluene, and chlorobenzene molecules on the Si(1 1 1)-7 × 7 surface. Through time-lapse STM imaging and automated image analysis we probe both the chemisorbed and the physisorbed states of these molecules. For the chemisorption to physisorption transition there are distinct site-specific variations in the measured rates, however their kinetic origin is ambiguous. There is also significant variation in the competing rates out of the physisorbed state into chemisorption at the various surface sites, which we attribute to differences in site-specific Arrhenius pre-factors. A prediction of the outcome of the competing rates and pre-factors for benzene over three hours matches experiment.

Enhanced immobilization of gold nanoclusters on graphite.

The immobilization of individual biological molecules by metal nanoparticles requires that the particles themselves be immobilized. We introduce a new technique for immobilization of gold clusters based on their binding to small tunnels in a graphite support, themselves created by the implantation of small clusters. These tunnels are shown to perform as more effective cluster immobilization sites than point defects on the surface of graphite. The method is tested with atomic force microscopy (AFM) (both contact and noncontact mode) scanning. Size-selected clusters with 923, 561, 309, and 147 atoms have been immobilized and imaged with high-resolution, noncontact AFM.

How nanoscience translates into technology: the case of self-assembled monolayers, electron-beam writing, and carbon nanomembranes.

One of the great quests in nanotechnology is to translate nanoprecision materials science into practical manufacturing processes. The paper by Angelova et al. in this issue of ACS Nano, which discusses the production of functional carbon-based membranes with a thickness of 0.5 to 3 nm, provides instructive insight into how researchers are pulling together complementary strands from a quarter century of nanoscience research to develop novel, hybrid processing schemes. In this Perspective, we reflect on the progress that is taking place in the two principal component technologies combined in this scheme, namely, (i) control of self-assembled monolayers, including their detailed atomic structures, and (ii) electron-induced manipulation and processing of molecular layers, as well as considering (iii) remaining challenges for thin membrane production in the future.

Experimental evidence for fluctuating, chiral-type Au55 clusters by direct atomic imaging.

We report the atomic-scale structures and fluctuating dynamical behavior of size-selected Au(55) clusters obtained by aberration-corrected scanning transmission electron microscopy (STEM) coupled with systematic STEM simulations. No high-symmetry structures (face-centered cubic polyhedron, icosahedron, or decahedron) were observed in our statistical investigation. We find Au(55) clusters that are characteristic of the theoretically predicted chiral structure and similar sister isomers (which together we define as the chiral structural zone). The chiral structural zone was found to arise repeatedly in the time-lapse sequences of images we measured, though other amorphous-like structures are also frequently observed. The approach demonstrated here can be applied to identify specific low-symmetry atomic structures in other small clusters and distinguish them unambiguously from high-symmetry isomers.

Preparing and regulating a bi-stable molecular switch by atomic manipulation.

We present a scanning tunneling microscopy (STM) investigation into the influence of the STM tip on the adsorption site switching of polychlorinatedbiphenyl (PCB) molecules on the Si(111)-7 × 7 surface at room temperature. From an initially stable adsorption configuration, atomic manipulation by charge injection from the STM tip prepared a new bi-stable configuration that switched between two bonding arrangements. No switching rate bias dependence was found for +1.0 to +2.2 V. Assuming a thermally driven switching process we find that the measured energy barriers to switching are influenced by the exact location of the STM tip by more than 10%. We propose that this energy difference is due the dispersion interaction between the tip and the molecule.

Determination of the ground-state atomic structures of size-selected au nanoclusters by electron-beam-induced transformation.

The equilibrium ground state atomic structures of nanoparticles are critical to understanding the relationship between their structure and functionality, e.g., in catalysis, and are the standard output of first principles and semiempirical theoretical treatments. We demonstrate a method of obtaining a stable population of the structural isomers of supported Au clusters from a metastable initial array via electron beam irradiation. Statistical investigation of size-selected Au clusters containing 923±23 atoms via aberration-corrected scanning transmission electron microscopy shows that virtually all of the icosahedral (Ih) clusters undergo structural transformations into decahedral (Dh) (primarily) or fcc isomers while Dh and FCC clusters generally retain their atomic structures after electron irradiation of each cluster individually for up to 400 s at a dose of 2.4×10(4) e-/angstrom2/frame. Intermediate phases are often observed in the image series (videos) before the appearance of the new stable isomers, the relative structural populations of which can be controlled via the electron beam dose. The comprehensive results reported here should provide a valuable experimental reference for testing or refining potential models and for kinetic or dynamical treatments of the atomic configurations.

Direct atomic imaging and dynamical fluctuations of the tetrahedral Au(20) cluster.

We report real-space, atomic-resolution images of Au(20) clusters obtained with the aberration-corrected Scanning Transmission Electron Microscopy. The proposed tetrahedral (FCC segment) pyramid structure is confirmed. The clusters cycle between isomers under the electron beam in the time-lapse images acquired. Disordered variants on the high symmetry forms are commonly observed. We believe that the direct experimental identification of these kinds of atomic structure, and the fluctuations between them, is fundamental to our understanding of nanoparticle structures, as well as applications such as heterogeneous catalysis.

Transcriptional response to GAA deficiency (Pompe disease) in infantile-onset patients.

Pompe disease is a genetic disorder resulting from a deficiency of lysosomal acid alpha-glucosidase (GAA) that manifests as a clinical spectrum with regard to symptom severity and rate of progression. In this study, we used microarrays to examine gene expression from the muscle of two cohorts of infantile-onset Pompe patients to identify transcriptional differences that may contribute to the disease phenotype. We found strong similarities among the gene expression profiles generated from biceps and quadriceps, and identified a number of signaling pathways altered in both cohorts. We also found that infantile-onset Pompe patient muscle had a gene expression pattern characteristic of immature or regenerating muscle, and exhibited many transcriptional markers of inflammation, despite having few overt signs of inflammatory infiltrate. Further, we identified genes exhibiting correlation between expression at baseline and response to therapy. This combined dataset can serve as a foundation for biological discovery and biomarker development to improve the treatment of Pompe disease.

Mass spectrometry and dynamics of gold adatoms observed on the surface of size-selected Au nanoclusters.

We report the imaging, mass spectrum, and dynamical behavior of adatoms and small clusters observed on the surface facets of size-selected, truncated octahedral gold clusters, Au(N) (N = 923 ± 23), via aberration-corrected scanning transmission electron microscopy. Our quantitative atom counting measurements show that most (~70%) of the species on the surface are single Au adatoms. Such species are now proposed as key elements of the atomic structure of both monolayer-protected nanoclusters (nanoparticles) and self-assembled monolayers and may also play a role in gold nanocatalysis. The adatoms are found on both {100} and {111} facets with similar probabilities.

Site- and energy-selective intramolecular manipulation of polychlorinated biphenyl (PCB) molecules.

We demonstrate the conversion of an adsorbed precursor state of polychlorinated biphenyl (PCB) molecules on the Si(111)-7 × 7 surface at room temperature into a more stable configuration via site- and energy-selective atomic manipulation in the scanning tunneling microscope (STM). Whereas molecular desorption is maximized by electron injection into the chemisorbed molecular ring at low voltage, injection into the physisorbed molecular ring above a threshold voltage (2.5 V) favors the reconfiguration of the bonding. The results clearly demonstrate both intramolecular charge localization and intramolecular charge transportation as key ingredients in the atomic manipulation of individual polyatomic molecules.

Nonlocal desorption of chlorobenzene molecules from the Si(111)-(7×7) surface by charge injection from the tip of a scanning tunneling microscope: remote control of atomic manipulation.

We report the nonlocal desorption of chlorobenzene molecules from the Si(111)-(7×7) surface by charge injection from the laterally distant tip of a scanning tunneling microscope and demonstrate remote control of the manipulation process by precise selection of the atomic site for injection. Nonlocal desorption decays exponentially as a function of radial distance (decay length ∼100 A) from the injection site. Electron injection at corner-hole and faulted middle adatoms sites couples preferentially to the desorption of distant adsorbate molecules. Molecules on the faulted half of the unit cell desorb with higher probability than those on the unfaulted half.